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Phase analysis of the solidified KF–(LiF–NaF–UF4)–ZrF4 molten electrolytes for the electrowinning of uranium

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Abstract

The X-ray diffraction (XRD) phase analysis of different solidified uranium-based fluoride systems ((LiF–NaF)eut–UF4; (KF–LiF–NaF)eut–UF4; (LiF–NaF)eut–UF4–ZrF4 and (KF–LiF–NaF)eut–UF4–ZrF4) were examined in order to provide the basis for pyro-electrochemical extraction of uranium in molten fluorides. Several uranium-based species (Na2UF6, Na3UF7, K2UF6, K3UF7, UO2, K3UO2F5) were identified in the solidified melts. The role of oxygen in argon atmosphere was found to be critical in the formation of uranium species during the melting and solidification. In order to reduce the accumulated level of free oxygen traces in our experiments, zirconium (in the form of ZrF4) was used inside the melt as an oxygen buffer. It was found that ZrF4 can really stabilize the uranium species by complexation and protects them against the oxygenation. The results of this work highlight the importance of oxygen removal for obtaining pure deposit in the electrorefinning of uranium.

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Acknowledgments

The Radioactive Waste Repository Authority (RAWRA, Czech Republic) and ACSEPT (EUROATOM FP7 EC) are acknowledged for financial support. This work was also supported by the Science and Technology Assistance Agency under contract No. APVV–0460–10, by the Slovak Grant Agency Vega 2/0116/14 and VEGA 2/0095/12 and by the SUSEN Project CZ.1.05/2.1.00/03.0108 of the European Regional Development Fund.

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Authors and Affiliations

  1. Fluorine Chemistry Department, Nuclear Research Institute (NRI) Řež Plc., Husinec-Řež 130, 250 68, Řež, Czech Republic

    M. Korenko, M. Straka, J. Uhlíř & L. Szatmáry

  2. Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9, 845 36, Bratislava, Slovakia

    M. Korenko & M. Šimurda

  3. Research Centre Řež, Husinec-Řež 130, 250 68, Řež, Czech Republic

    J. Uhlíř

  4. Department of Inorganic Chemistry, Technology and Materials, Slovak University of Technology, Radlinskeho 9, 812 37, Bratislava, Slovakia

    M. Ambrová

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  1. M. Korenko
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  2. M. Straka
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  3. J. Uhlíř
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  4. L. Szatmáry
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  5. M. Ambrová
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Correspondence to M. Korenko.

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Korenko, M., Straka, M., Uhlíř, J. et al. Phase analysis of the solidified KF–(LiF–NaF–UF4)–ZrF4 molten electrolytes for the electrowinning of uranium. J Radioanal Nucl Chem 302, 549–554 (2014). https://doi.org/10.1007/s10967-014-3219-6

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  • DOI: https://doi.org/10.1007/s10967-014-3219-6

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